Joint ICTP/CAS/IAEA School & Workshop on Plasma-Materials Interaction in Fusion Devices, July 18-22, 2016, Hefei Introduction to First-Principles Method by Guang-Hong LU （吕广宏） Beihang University Computer Modeling & Simulation Theory ComputerComputer modeling & simulation” has Modeling emerged as an indespensableExperiment method for & scientificSimulation research of materials in parallel to experiment and theory. Outline Introduction (first principles) Introduction (history of first principles) Basic principles • calculation of total energy • electron-electron interaction (DFT-LDA) • Bloch’s theorem – periodic system • electron-ion interaction (pseudopotential) Supercell technique Computational procedure Future 3 Multiscale Modeling & Simulation： Conceptual framework First-principles method First-principles method Solve quantum mechanic Schrodinger equation to obtain Eigen value and Eigen function, and thus the electronic structure. • The charm: only atomic number and crystal structure as input, which can determine precisely the structure and the properties of the real materials. • first principles - physics, materials Density functional theory • ab initio -quantum chemistry Hartree-Fork self-consistent field A connection between atomic and macroscopic levels （不同尺度之间的联系） First-principles method Elastic constants Binding energy Energy barrier mechanics thermodynamics kinetics 7 Outline Introduction (first principles) Introduction (history of first principles) Basic principles • calculation of total energy • electron-electron interaction (DFT) • Bloch’s theorem – periodic system • electron-ion interaction (pseudopotential) Supercell technique Computational procedure Future 8 Development of quantum theory in the past 100 years 过去100年量子理论的历史 1920s-1930s The foundation for most of the theories 1960s Accurate band structures 1970s Surfaces and interfaces 1980s Structural and vibrational properties 1990s Applications to complex and novel materials Materials physics Slow! Atomic physics Fast! 9 Difficulties in solving the Schrödinger equation • Dirac (1929): The difficulty is only that the exact application of quantum theory leads to equations much too complicated to be soluble. • Large number of strongly interacting atoms in a solid Schrödinger equation： Simple to write, yet hard to solve equation • Calculation in the past 100 years: Physical models and theories to simplify of the equations first principles Origin：the first mover Newton’s first law: an object either remains at rest or continues to move at a constant velocity, unless acted upon by a net force. If all the objects were at rest at the start of the universe, yet they moved later. What is the origin of their movement? Newton believes this is moved by the God, “the first mover”. The first mover should base on one principle, called “first principle” Quantum mechanics theory– first principle quantum mechanics reflects structure of atom & molecule and thus the properties of matter, such theory approximates the principle that reflects nature of the universe. 11 first principles According to the interaction between nucleus and electrons based on quantum mechanics principles, first principles method finds the solution to the Schrodinger equation through series of approximations and simplifications. 1D Schrodinger equation Wave function 3D Schrodinger equation Eigen value, Eigen function Stationary Schrodinger equation Energy, electron density Outline Introduction (first principles) Introduction (history of first principles) Basic principles • calculation of total energy • electron-electron interaction (DFT) • Bloch’s theorem – periodic system • electron-ion interaction (pseudopotential) Supercell technique Computational procedure Future 13 Total energy Nearly all physical properties are related to total energies or to differences between total energies. • Equilibrium lattice constant: energy minimum • surfaces, interfaces and defects, nanostucture: structure that minimize the total energy • force: derivative of energy with respect to a position • stress: derivative of energy with respect to a strain • elastic constant: second derivative of energy If total energies can be calculated, any physical properties that can be related to a total energy or a difference between total energies can be determined computationally. 14 Total energy calculations First-principles methods • compute the total energy of a system of electrons and nuclei • a subsequent minimization of the energy with respect to the electronic and nuclear coordinates. Technique: constructing a Hamiltonian • kinetic energy of particles • Coulomb interactions between all the particles Total-energy calculations: simplifications and approximations needed • many-body system: nuclei and electrons • computation: formidable 15 The basic approximation: Separation of electron and nucleus Electrons respond essentially instantaneously to the motion of the nuclei • - Electron and nucleus: large difference in mass Separate of electronic and nuclear coordinates in the many-body wave function Born-Oppenheimer approximation (Adiabatic principle) 16 Total energy calculation • Five parts consist of total energy 1 Total energy Electronic Electron-electron Electron Electron-ion Kinetic energy (Coulomb) (many-body) (Coulomb) Ion-ion Exchange-correlation -xc Pseudopotential Hartree (nucleus-nucleus) DFT-LDA(GGA) approximation Madelung Energy 2 3 4 5 17 Total energy calculation • Five parts consist of total energy 1 Total energy Electronic Electron-electron Electron Electron-ion Kinetic energy (Coulomb) (many-body) (Coulomb) Ion-ion Exchange-correlation -xc Pseudopotential Hartree (nucleus-nucleus) DFT-LDA(GGA) approximation Madelung Energy 2 3 4 5 18 Outline Introduction (first principles) Introduction (history of first principles) Basic principles • calculation of total energy • electron-electron interaction (DFT) • Bloch’s theorem – periodic system • electron-ion interaction (pseudopotential) Supercell technique Computational procedure Future 19 Electron-electron interaction: Density functional theory Exchange-correlation • exchange: energy reduction due to a spatial separation between the electrons with the same spin • correlation: energy reduction due to a spatial separation between the electrons with the opposite spin Density Functional Theory (DFT) • strongly interacting electron gas a single particle moving in an effective potential • (one-electron or mean-field approximation) • Hohenberg and Kohn (1964), Kohn and Sham (1965) 20 Density functional theory Total energy: a unique functional of electron density The minimum value of the total energy functional is the ground-state energy of the system, and the density that yields this minimum value is the exact single- particle ground-state density. (Hohenberg and Kohn, 1964) How to replace the many-electron problem by an exactly equivalent set of self-consistent one-electron equations. (Kohn and Sham, 1965) 21 Density functional theory formulations • Kohn-Sham equation (Redberg a.u.) 2 Veff (r) i (r) i i (r) Veff (r) Vion (r) VH (r) xc (r) 2n(r') V (r) dr 3 (Hartree potential) H r r' E (n) (r) xc (exchange - correlation potential) xc n occ 2 n(r) i (r) (electron density) i 22 Local density approximation • Exchange-correlation energy: exchange-correlation energy per electron in a homogeneous electron gas with the same density as the electron gas at point r. hom xc (r) xc [n(r)] E (n) (r)n(r)dr 3 xc xc (r) (r) n(r) xc xc xc n 23 LDA examples Perdew-Zunger type Wigner type 0.4582?2 ε =ε +ε , ε =- xc x c x r s 0.4582 2 , -0.1423?2 xc x c x r ?1 rs 1+1.0529 r +0.3334 r s ss 0.88 c εc = r 7.8 s (-0.0480+0.0311 lnrss -0.0116r rd s xc +0.0020r lnr )? 2 r <1 xc xc s s s 3 drs δεxcrd sε xc μxc=ε xc+ρ =ε xc - δρ 3 drs 1 3 3 点 的电子密度 1 Charge densityrr at point r (r) , s 4 24 Generalized Gradient Approximation (GGA) LDA fails in situations where the density undergoes rapid changes. GGA: considering the gradient of the electron density xc(r ) xc [ n ( r ), n ( r )] • A commonly used functional: PW91 • (Perdew and Yang,1992) 25 Total energy formulations 1 E T()()()()()() n V r n r dr33 V r n r dr E n E total ion2 H xc i i occ (r ) 2 ( r ) dr 3 V ( r ) n ( r ) dr 3 i i ion i 1 2n ( r ) n ( r ') dr3 dr' 3 ( r ) n ( r ) dr 3 E 2'rr xc i i 26 Difficulties after DFT DFT: Many-body an effective single-particle interaction Computation: a formidable task • infinite number of noninteracting electrons in a static potential of an infinite number of nuclei or ions. Two difficulties • a wave function must be calculated for each of the infinite number of electrons in the system • since each electronic wave function extends over the entire solid, the basis set required to expand each wave function is infinite. 27 Outline Introduction (first principles) Introduction (history of first principles) Basic principles • calculation of total energy • electron-electron interaction (DFT) • Bloch’s theorem – periodic system • electron-ion interaction (pseudopotential) Supercell technique Computational procedure Future 28 Bloch’s theorem Bloch’s theorem: in a periodic solid, each electronic wave function can be written as the product of a cell-periodic part and a wavelike part r exp( ik r ) u ( r ) (r R ) exp( ik R ) (r ) Real space, reciprocal space 2 i=j abi j 2 ij 0 i j Wave function can be calculated only in a primitive cell 29 k points sampling The electronic wave functions at k points that are very close together Bloch theorem: will be almost identical,